# US 7,743,738 B2 · Scavenging phosphorus, sulfur, and lead from combustion exhaust using tungsten compounds and lubricant

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- Number: US 7,743,738 B2
- Document ID: US7743738B2
- Status: Granted
- Kind: B2
- Application number: 11/680,752
- Filed: 2007-03-01
- Published: 2008-09-04
- Granted: 2010-06-29
- Earliest claimed: 2007-03-01
- Assignees: Afton Chemical Corporation
- Inventors: Dennis H. Rainear; Allen A. Aradi; Joseph W. Roos
- Web page: https://patentgrep.com/patent/US7743738B2

## CPC

- B01D 53/9445: {Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]}
- C10L 1/1216: {metal compounds, e.g. hydrides, carbides}
- C10L 10/02: for reducing smoke development
- C10L 10/04: for minimising corrosion or incrustation
- C10L 10/06: for facilitating soot removal
- C10M 141/12: at least one of them being an organic compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
- F01N 3/029: by adding non-fuel substances to exhaust
- F23J 7/00: Arrangement of devices for supplying chemicals to fire
- B01D 2255/20776: Tungsten
- B01D 2258/012: Diesel engines and lean burn gasoline engines
- C10M 2219/00: Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M 2223/045: Metal containing thio derivatives
- C10M 2223/047: Thioderivatives not containing metallic elements
- C10M 2223/049: Phosphite
- C10N 2010/12: Groups 6 or 16
- C10N 2030/74: {Noack Volatility}
- Y02A 50/20: Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
- Y02T 10/12: Improving ICE efficiencies
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- C10L: FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
- C10M: LUBRICATING COMPOSITIONS (well drilling compositions C09K8/02); USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION (mould release, i.e. separating, agents for metals B22C3/00, for plastics or substances in a plastic state, in general B29C33/56, for glass C03B40/02; textile lubricating compositions D06M11/00, D06M13/00, D06M15/00; immersion oils for microscopy G02B21/33)
- F01N: GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES (arrangements in connection with gas exhaust of propulsion units in vehicles B60K13/00; combustion-air intake silencers specially adapted for, or arranged on, internal-combustion engines F02M35/00; protecting against, or damping, noise in general G10K11/16)
- F23J: REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES (combustion apparatus for consuming smoke or fumes, e.g. exhaust gases, F23G7/06)
- C10N: INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- Y02A: TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02T: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION

## Abstract

The present invention relates to an apparatus and method for delivering tungsten into a fuel combustion system or to the exhaust therefrom. By the present invention, tungsten from the lubricant or the fuel will interact with combustion products and, in particular, phosphorus, sulfur, and/or lead from the combustion products. In this manner, the tungsten scavenges or inactivates harmful materials which have migrated into the fuel or combustion products, and which can otherwise poison catalytic converters, sensors and/or automotive on-board diagnostic devices The present invention can also lead to improved durability of exhaust after treatment systems. A lubricant in accordance with the present invention is also disclosed.

## Claims

### Claim 1

In a combustion system that combusts a hydrocarbonaceous fuel and a lubricant to produce an exhaust stream comprising at least one contaminant selected from a group consisting of phosphorous, lead, sulfur, and compounds thereof, a method for reducing deleterious effects of the at least one contaminant on an after treatment and/or a control device, comprising:
via a tungsten source, adding tungsten to the lubricant;
wherein the lubricant comprises a major amount of a base oil of lubricating viscosity and a minor amount of at least one additive selected from a group comprising at least one of an organosulfur compound and an organophosphorous compound,
wherein the tungsten source is selected from a group comprising elemental tungsten, organotungsten, tungsten oxide, sulphur-containing organotungsten, sulphur- and phosphorus-free tungsten compounds, tungsten acids, tungsten trioxide, ammonium ortho tungstate, ammonium metal tungstate, ammonium paratungstate, sodium tungstate, potassium tungstate, tungsten halides, tungsten hexacarbonyl, tungsten ethoxide, tungsten oxychloride, tungsten pentacarbonyl-N-pentylisonitrile, tungsten silicide, cyclomatic tungsten compounds, tungsten organoamines, tungsten phosphenes, organo-oxo-tungstenates, MgWO4, CaWO4, and ZnWO4;
combusting the hydrocarbonaceous fuel and the lubricant in the combustion system, thereby producing the exhaust stream;
during or after the combusting, exposing the tungsten to the at least one contaminant;
during or after the combusting, scavenging at least some of the at least one contaminant; and
as a result of the scavenging, reducing contact between the at least one contaminant and the after treatment system and/or the control device, thereby reducing the deleterious effects of the at least one contaminant on the after treatment system and/or the control device.

### Claim 2 (depends on 1)

The method of claim 1, wherein the at least one contaminant originates from the fuel.

### Claim 3 (depends on 1)

The method of claim 1, wherein the at least one contaminant originates from air used in the combustion.

### Claim 4 (depends on 1)

The method of claim 1, wherein the at least one contaminant originates from the lubricant.

### Claim 5 (depends on 1)

The method of claim 1, wherein the exhaust stream is essentially free of phosphorus and compounds thereof following scavenging.

### Claim 6 (depends on 1)

The method of claim 1, wherein the after treatment system comprises at least one selected from a group comprising a catalytic converter, a three-way catalytic converter a lean NOx trap, a catalyzed diesel particulate filter, a diesel oxidation catalyst, a continuously regenerating technology diesel particulate filter, an O2 sensor, and an NOx sensor.

### Claim 7 (depends on 1)

The method of claim 1, wherein the control device comprises at least one selected from a group comprising a sensor and an on-board diagnostic device.

### Claim 8 (depends on 1)

The method of claim 1, wherein the combustion system comprises at least one selected from a group consisting of a diesel-electric hybrid vehicle, a gasoline-electric hybrid vehicle, a two-stroke engine, stationary burners, waste incinerators, diesel fuel burners, diesel fuel engines, automotive diesel engines, gasoline fuel burners, gasoline fuel engines, power plant generators, internal and external combustion devices, machines, engines, turbine engines, jet engines, boilers, incinerators, evaporative burners, plasma burner systems, a plasma arc, stationary burners, and devices that can combust or in which can be combusted a hydrocarbonaceous fuel.

### Claim 9 (depends on 1)

The method of claim 1, wherein the hydrocarbonaceous fuel is selected from a group consisting of diesel fuel, biodiesel, biodiesel-derived fuel, synthetic diesel, jet fuel, alcohols, ethers, kerosene, low sulfur fuels, synthetic fuels, Fischer-Tropsch fuels, fuels derived from coal, genetically engineered biofuels and crops and extracts therefrom, natural gas, propane, butane, unleaded motor and aviation gasolines, reformulated gasolines which contain both hydrocarbons of the gasoline boiling range and fuel-soluble oxygenated blending agents, gasoline, bunker fuel, coal (dust or slurry), crude oil, used engine or motor oils, refinery “bottoms” and by-products, crude oil extracts, hazardous wastes, yard trimmings and waste, wood chips and saw dust, agricultural waste, fodder, silage, plastics, organic waste, and mixtures thereof, and emulsions, suspensions, and dispersions thereof in water, alcohol, and other carrier fluids.

### Claim 10 (depends on 1)

An apparatus for performing the method of claim 1, said apparatus comprising:
(a) a combustion chamber adapted to combust the hydrocarbonaceous fuel and the lubricant:
(b) a means to introduce the hydrocarbonaceous fuel and the lubricant into the combustion chamber;
(c) a means to convey the exhaust stream from the combustion chamber; and
(d) a means to introduce the lubricant to the exhaust stream.

### Claim 11 (depends on 10)

The apparatus of claim 10, wherein the after treatment system comprises at least one selected from a group comprising a catalytic converter, a three-way catalytic converter, a lean NOx trap, a catalyzed diesel particulate filter, a continuously regenerating technology diesel particulate filter, an O2 sensor, and an NOx sensor.

### Claim 12 (depends on 10)

The apparatus of claim 10, wherein the control device comprises at least one selected from a group comprising a sensor and an on-board diagnostic device.

### Claim 13 (depends on 10)

The apparatus of claim 10, wherein the apparatus comprises at least one selected from a group consisting of a diesel-electric hybrid vehicle, a gasoline-electric hybrid vehicle, a two-stroke engine, stationary burners, waste incinerators, diesel fuel burners, diesel fuel engines, automotive diesel engines, gasoline fuel burners, gasoline fuel engines, power plant generators, internal and external combustion devices, machines, engines, turbine engines, jet engines, boilers, incinerators, evaporative burners, plasma burner systems, a plasma arc, stationary burners, and devices that can combust or in which can be combusted a hydrocarbonaceous fuel.

### Claim 14

A method for improving the durability of an after treatment device for a combustion system, said method comprising:
selecting a tungsten source from a group consisting of elemental tungsten, organotungsten, tungsten oxide, sulphur-containing organotungsten, sulphur- and phosphorus-free tungsten compounds, tungsten acids, tungsten trioxide, ammonium ortho tungstate, ammonium metal tungstate, ammonium paratungstate, sodium tungstate, potassium tungstate, tungsten halides, tungsten hexacarbonyl, tungsten ethoxide, tungsten oxychloride, tungsten pentacarbonyl-N-pentylisonitrile, tungsten silicide, cyclomatic tungsten compounds, tungsten organoamines, tungsten phosphenes, organo-oxo-tungstenates, MgWO4, CaWO4, and ZnWO4;
combusting a hydrocarbonaceous fuel and a lubricant in the combustion system;
as a result of the combusting, producing a combustion product containing at least one contaminant selected from a grout) consisting of phosphorous, sulfur, lead, and compounds thereof;
introducing tungsten, via the tungsten source, into at least one of the hydrocarbonaceous fuel or the lubricant in an amount sufficient for the tungsten to interact with the at least one contaminant;
with the tungsten, scavenging at least some of the at least one contaminant from the combustion product:
as a result of the scavenging, reducing contact between the at least one contaminant and the after treatment device, thereby improving the durability of the after treatment device.

### Claim 15 (depends on 14)

The method of claim 14, wherein the amount of phosphorus detected on the after treatment device is reduced by an amount of from 20% to 80% by weight, relative to the amount of phosphorus detected if the tungsten is not contacted with the combustion product.

### Claim 16 (depends on 14)

The method of claim 14, wherein the amount of sulfur detected on the after treatment device is reduced by an amount of from 20% to 80% by weight, relative to the amount of sulfur detected if the tungsten is not contacted with the combustion product.

### Claim 17 (depends on 14)

The method of claim 14, wherein the amount of lead detected on the after treatment device is reduced by an amount of from 20% to 80% by weight, relative to the amount of lead detected if the tungsten is not contacted with the combustion product.

### Claim 18 (depends on 1)

The method of claim 1, wherein the organosulfur compound in the lubricant is selected from a group consisting of sulfurized olefins, sulfurized fats and vegetable oils, sulfurized unsaturated esters and amides, ashless and metal containing dithiocarbamates, substituted thiadiazoles, sulfurized hindered phenols, sulfurized alkylphenols, neutral metal-containing sulfonate detergents, overbased metal-containing sulfonate detergents, neutral metal-containing sulfurized phenate detergents, and overbased metal-containing sulfurized phenate detergents, or combinations and mixtures thereof.

### Claim 19 (depends on 1)

The method of claim 1, wherein the organophosphorus compound in the lubricant is selected from a group consisting of primary, secondary and aryl neutral and overbased zinc dialkyldithiophosphates (ZDDP's), trialkyl- and triarylphosphites, mixed alkyl/aryl phosphites, alkyl and aryl phosphorothiolthionates, and alkyl and aryl phosphorothionates, and combinations or mixtures thereof.

### Claim 20 (depends on 1)

The method of claim 1, wherein the base oil is selected from a group consisting of paraffinic, naphthenic, aromatic, poly-alpha-olefins, synthetic esters, and polyol esters, and mixtures thereof.

### Claim 21 (depends on 1)

The method of claim 1, wherein the base oil contains less than or equal to 0.03 wt. % sulfur, and greater than or equal to 90 wt. % saturates, and has a viscosity index greater than or equal to 80 and less than or equal to 120.

### Claim 22 (depends on 1)

The method of claim 1, wherein the base oil contains less than or equal to 0.03 wt. % sulfur, and greater than or equal to 90 wt. % saturates, and has a viscosity index greater than or equal to 120.

### Claim 23 (depends on 1)

The method of claim 1, wherein the base oil is substantially sulfur-free.

### Claim 24 (depends on 1)

The method of claim 1, wherein the hydrocarbonaceous fuel contains low levels of sulfur.

### Claim 25 (depends on 1)

The method of claim 1, wherein the hydrocarbonaceous fuel is substantially free of sulfur.

### Claim 26 (depends on 1)

The method of claim 1, wherein the hydrocarbonaceous fuel contains low levels of sulfur and is further treated with oxygenates.

### Claim 27 (depends on 1)

The method of claim 1, wherein the hydrocarbonaceous fuel is substantially free of sulfur and is further treated with oxygenates.

### Claim 28

A method of improving the combustion of a fuel in a combustion system, as determined by reduced thermal gravimetric analysis light-off temperature of combustion particulate products, said method comprising:
lubricating a combustion system with a lubricant comprising a major amount of a base oil of lubricating viscosity and a minor amount at least one tungsten source;
introducing tungsten to the combustion in the combustion system of the fuel;
selecting the fuel from the group consisting of diesel fuel and motor and aviation gasolines;
with the tungsten, scavenging at least some of at least one contaminant from the combustion product, wherein the at least one contaminant is selected from a group consisting of phosphorous, sulfur, lead, and compounds thereof;
as a result of the scavenging, reducing the thermal gravimetric analysis light-off temperature of combustion particulate products in the presence of tungsten relative to the thermal gravimetric analysis light-off temperature of combustion particulate products in the absence of tungsten, thereby improving the combustion of the fuel in the combustion system.

### Claim 29

A method to inhibit the formation of a phosphorus-containing, sulfur-containing, or lead-containing permeability-reducing glaze on the surface of a catalyst exposed to the products from the combustion in a combustion unit of a fuel, said method comprising:
adding tungsten to at least one of the fuel or a lubricant for the combustion unit;
contacting the tungsten or compounds thereof with the products of combustion of the fuel, wherein the combustion products contain at least one contaminant selected from the group consisting of phosphorus-containing, sulfur-containing and lead-containing materials;
scavenging the at least one contaminant from the combustion products via the tungsten; and
due to the scavenging, inhibiting the formation of a permeability-reducing glaze containing the at least one contaminant on a surface of a catalyst exposed to the products of combustion of the fuel.

### Claim 30

A method for reducing the deleterious effect on exhaust emissions after treatment and control devices of at least one contaminant selected from the group consisting of phosphorus, lead, sulfur and compounds thereof in an exhaust stream from the combustion of a hydrocarbonaceous fuel containing a tungsten compound in a combustion system, said method comprising:
combusting in the combustion system the hydrocarbonaceous fuel containing the tungsten compound to produce combustion products comprising at least one material selected from the group consisting of sulfur, lead, phosphorus, and compounds thereof,
scavenging at least one of the contaminants selected from the group consisting of sulfur, lead, phosphorus, and compounds thereof via the tungsten, and
as a result of the scavenging, reducing contact between the at least one contaminant and the after treatment system and the control devices, thereby reducing the deleterious effect of the at least one contaminant on the after treatment system and control devices.

### Claim 31

A lubricating oil composition comprising:
an oil of lubricating viscosity,
at least one additive selected from a group comprising at least one of an organosulfur compound and an organophosphorous compound,
a detergent,
an amount of a metal dihydrocarbyldithiophosphate compound,
at least one tungsten compound in an amount sufficient to provide the composition with at least 10 ppm of tungsten,
wherein the tungsten compound selected from a group comprising elemental tungsten, organotungsten, tungsten oxide, sulphur-containing organotungsten, sulphur- and phosphorus-free tungsten compounds, tungsten acids, tungsten trioxide, ammonium ortho tungstate, ammonium metal tungstate, ammonium paratungstate, sodium tungstate, potassium tungstate, tungsten halides, tungsten hexacarbonyl, tungsten ethoxide, tungsten oxychloride, tungsten pentacarbonyl-N-pentylisonitrile, tungsten silicide, cyclomatic tungsten compounds, tungsten organoamines, tungsten phosphenes, organo-oxo-tungstenates, MgWO4, CaWO4, and ZnWO4, and
an effective amount of a friction modifier,
wherein said composition has a Noack volatility of about 15 wt % or less.

### Claim 32 (depends on 31)

The composition of claim 31, wherein said tungsten from the at least one tungsten compound is present in an amount of about 10 ppm to about 750 ppm.

### Claim 33 (depends on 32)

The composition of claim 32, wherein the tungsten is present in an amount of about 10 ppm to about 350 ppm.